Sulfur dyestuffs and process of making same.



.-'iTED sT Tns PATENT-1 OFFICE.

'WILHELMHAHNENKAMM, or smnnmenu, NEAR HUQHST -ONeTHE-MAiN ;GERMANY,

ASSIGNOR To. FARBWERKE VORM. MEISTER LUGIUS & BRUNING,'.oF I-weHs'r-oN- THE-MAI1\T, GERMANY, ACORPORATIQN .O'F GERMANY.

SULFUR DYESTUFFS AND" rRooEss or MAKIN l No Drawing.

To all whom it may concern.- Y

Be it known that I, Wl'nimnu HAHNEL TKAMM, Ph. D.,'chemist, a citizen of the E111 pire of Germany, residnig at Sindhngen,

near Hiichston-the-Main, Germany, have value canbe'obtained from. theindophenolsulfonic acids, which can be produced. either by condensing" nitrosophenol or its substitution products, or oxidizing p-aminophenol or its substitution products, with the prod-. ucts resulting from the condensation of a para-diamin with a naplithylaminsulfonicacid. For this purpose,-the said indopher nols are treated with alkali-polysulfids, with o'r.witl1out copper salts, or copper, or any other metallic salt.

The condensation products from which the new indophenolsulfonic acids are derived can be. obtained, according'to U. S.'

patent application Ser. No. 682,282, filed ihliai-ch"7th; 1912, by fusing para-diamins (under which term are to be comprised both the mononuclear p-diannns, such as p-phenyleneor toluylenedlamins,- and naphthylenediamins or their substitution products, and the heteronuclear 'p-diannns, such as' the benzidins and their hom'ologues andsubstitution products, etc.) with naphth-ylaininsult'onic acids,- such for instance as 1.7 Y (or 1.8 or- 1.2-) naphthylaminsulfonic acid, 1.4.8-

jnaphthylaniindisulfonic acids or the like;

with or without-the addition of a solvent or a suspending agent. The mode of-operation may for instance be as follows: 44.6 kg. of

a-naphthylamin-Sssulfonic acid and 55.2 kg.

of benzidin are heated together and the melt thus obtained is lib'erated'in a finely powderedcondition from the 1 admixture of henzidin and oz-naphthylamin-8-sulfon1c acid- 5' by repeatedly treating it withaboiling solution of sodium. carbonate and precipitating the boiling solution with diluted hydrochloric acid. i r

i The indopheno'l'sulfonic acids are produced in the usualnianner by simultaneously--oxidizing components yielding indophenols,

e -phenols containing in para-position to the hydroxyl group a group containing n trogen wh1ch, on condensation with am1ns,'1s cons.

Specification of Letters Patent. Application filed March 7, 191 2.

p v I Patented J 1914, Serial No.682,23 U h verted into nitrogen-bound in Iqiiinoi dal manner, including aminophenols and nitrosophehols, with the above-mentioned sulfonic' acids. These 'indophenolsulfonic acids constitute bodies which l are in's'o'li'ible in water and soluble in diluted caustic-sod" 7e.

aid

The sulfura tio'n- ("11f "r-inelt), offthe acids can be obtained atfivarying"tempera tunes with alkali-polysulfid' in various proportion, with or without the addition of a dih1ent:(water, alcohol, glycerin or thel'ike) .or of copper or of a metallic salt (for instance a-coppe'r salt)l The addition of copper or a copper saltf-has proved to-bepart-icularly suitable for producing green dye-stufl's'. whereas, when no copper or a copper derivative is" added, 'dyestt'lfl's' "of a Imor'e' blue togreenish-blue tint are obtained.

The new dyestuffs} m genera-l, fare dark powders, soluble in alkalisulfids'to alcohol, almost soluble-in concentrated*sulfuric acid to a'light 'bluesolution.turning,

when heated, to dark-blue. and dyeingcot-fl with 1.7-11aphthylliniinsulfonicacidn ai'e in-v troduced into-an aqueous so "tam ofpol sul- Zfid. consisting ofQSOQlig'i )f sodimii-sultid and 500 kg. ofsulfutihnd ieatediin-fltlle reflux-apparatus to b oilingffo,"a-bout"30 hours. with orwithoutthealdditiion of abet of sulfate of copper. Thetus'ionisconiplete can when no further inddphenolsulfdnic at d *be det'ected' thereinr? The isohitioir offthe d vestufi 'is effectedaccording to themethmls used in the manufactiire of sulfur dyestu'tt's,

for instance by extraction;precipitating by :1 current of air,"filtering pressure and drying. The dyestufi, thus obtained forms.

' whenin a purest-ate. a greenish-blue powder with a-metallic luster. readily dissolving in sodiumjsulfid-to a yellowish solution which dyes cottonbeautiful bright green tints, the fas'tness of which to. washing is much su'perior to that of the dyestuffs described in United States Patent No, 776.885. More over; the dyeings obtained by the new dyestufi possess an eminent fastness to light;

is'oli'i? non from whleh the leucoe'd vestufii n be. precipitated with common-salt. insohu e in Examinef11=3100fkgl 6f the whirled ip'henolsulfonic' -aeid produced oxidizing e product resulting from the condensation of p pheny'; 1

lenediaminwith, 1.8 napllthylaininsulfon-ic reflux-apparatus -to boiling for about hours-with or Without the addition-of about i 'The 'f-usipn is cording to the methods used in the manu jfactureyof sulfur dyestufi's, for instance by filtering .n ith'fpressure and drying. 1 f

extraction,'precipitating by a current of air,

apurcstate, a greenish-blue 'powderjwith a metallic luster, readily dissolving in sodium sulfid to a yellowishsolutionwhich dyes.

dvestufis ivhicli c omprises heating :with

cotton beautifulbright green tints; the fast ness ofiwhich to washing is'much superior to-thfat of the dyestu-fis Y described in United Stated Patent- No; 776,885,. ,Moreov'er the' he new dyestufis pOsdyeings d a ne'd by. l Sess an eminent f t I jxfnay be produced" in an an'alogous. nianhe'r-. f

' They "are remarkable for "their ready" solu- "bility an d 'their excellent .f stness tog-wash alkali polysulfidsthe indophenolsulf-onic acids obtainable from the; condensation products of p -dianiinsand 'naphthylamin- 'sulfonic acids,-- with phenols'containin'g in1 para-position to the hydroxyl group a' group @bnthining nitrogen Whichon condensat on with amins, isconverted into n-ltrogeniboundf iii quinoidal nia nn'er.

2. The process of an'ufa'c'turing, .sulf-ur alkali polysu'lfids ",the indophenols ulfonic acids obtainable from the condensation .products of :p-dia'mins and 'naphthyl'amin-. 4 sulfonic acids with -.aminophenols."

3.- The process '0 manufacturing sulfur which comprisesheating .with

rjanii'ns-and napthylamin' 1f I parwaminophenolsac1d,areintroduced intoan aqueous solutionof polysulfid, consisting of .800 kg. of sodium- P hthylaminsulfonic acids with i 'nophenols' j'dyestufl, obtainable-"by heating with "alkali polys'ulfids,,i n presence of .a derivative of new described ty aanagwha ',cop.per,the product resulting from the Conalllt'ali jpolysuliidginr ofa metallic salt, the indophenolsu foni acids obtainable .flfor m the condensation' p icts of :p diic acids with e j 4.'.ll1e*process' of manu ac uring sulfur dyestuffs, which consistsfin 4 heating with ralkal'ir olysulfids,in presence of a' metallic" 'salt andwhile addinga diluent, the indo'-.

[phendlsulfonic acids. obtainable? from the condensation products-,of' p-diamins and 5. As new productsblue to green sulfur dyestufi's obtainable by heat-mg with alkalithyla'm'insulfonic acids withvph'enolscontain- 'polysulfids the 'indophe-nolsulfonic acids ob tainablefrom the products'resulting from the condensation of "p-diamins and naph- The dyestuif 'thusobtained forms, when in ing in para-posi'tion'to the hydroxyl group group, containing nitrogen Which,"on condensati'on w th annns; s converted into "nitrogen @bound. in quinoid'al -.1 nanner,; said dyestuffs being dark powders, soluble alkali S'uliids to a" solution "from which the Leuco dyestu'flr' can be precipitatedwith comn onfsalt, insolubleinalcohol, almost soluble inQcohcentratedsulfUricacidto alight-blue The other sulfidfdyestufis of thisnew class,

solution-turning, when heated. to dark-blue,

s'olution fast blue to green tints.

6. As -fa. new"'pro'duct, he green sulfur yellowish solution from which the leuco-dye ,stufi? can be precipitated with common salt, insoluble in'.a1cohol,' almost soluble in concentratd sulfuric acid tea light blue SOluti'on turning, when he ated, to dark-blue, and

R. ;WI-LHELMQHAHNENKA5MM.-

Witnesses: I

5 "JEAN; GRUNi),

"CAR 6 m.

' dyeing Cotton from the sulfur-alkaline solu 

